CN104011184A

CN104011184A - Fuel compositions

Info

Publication number: CN104011184A
Application number: CN201280048813.7A
Authority: CN
Inventors: J.赖德
Original assignee: Innospec Ltd
Current assignee: Innospec Ltd
Priority date: 2011-08-03
Filing date: 2012-08-02
Publication date: 2014-08-27
Also published as: WO2013017887A1; KR20140063642A; CN107474885A; US20140174391A1; CA2843236A1; BR112014002539A2; CA2843236C; CN107474885B; AU2012291817A1; MY170245A; US9315753B2; BR112014002539B1; EP2554636A1; EP2739710A1; EP2739710B1; KR102002188B1; AR087946A1; AU2012291817B2

Abstract

A diesel fuel composition comprising, as an additive, the product of a Mannich reaction between: (a) an aldehyde; (b) an amine; and (c) a substituted phenol; wherein the phenol is substituted with at least one branched hydrocarbyl group having a molecular weight of between 200 and 3000; and wherein in the Mannich reaction used to form the additive the molar ratio of component (a) to component (b) is 2.2-1.01:1; the molar ratio of component (a) to component (c) is 1.99-1.01:1 and the molar ratio of component (b) to component (c) is 1:1.01-1.99.

Description

Fuel composition

The present invention relates to fuel composition and additive thereof.Especially, the present invention relates to the additive for diesel fuel composition, be particularly applicable to have those of modern diesel engine of high-pressure fuel system.

Due to consumer demand and rules, effectively many at the energy that becomes of diesel engine in recent years, show improved performance and there is the discharge of minimizing.

By the improvement in combustion processes, be created in these improvement in performance and in discharge.For realizing the required spraying of ruel of this improved burning, developed the fuel injection device in the fuel injector nozzle aperture of the higher spraying pressure of use and minimizing.Fuel pressure at injection nozzle surpasses 1500 bar (1.5 * 10 now conventionally ⁸pa).For reaching these pressure, must also improve to fuel work the temperature of fuel.These high pressure and temperatures can cause the deteriorated of described fuel.

The diesel engine with high-pressure fuel system can include but not limited to large diesel engine and less passenger car type diesel engine.Large diesel engine can comprise very powerful engine, for example, have MTU series 4000 diesel engine of 20 cylinder variants, and design is mainly used in ship and has the generating up to 4300kW power stage; Or such as the engines such as Renault dXi 7 with 6 cylinders and about 240kW power stage.Typical passenger vehicle diesel engine is Peugeot DW 10, and it has 4 cylinders and 100kW or lower power stage (depending on variant).

In about all diesel engine of the present invention, the general high-pressure fuel system that is characterized as.Normally, use and surpass 1350 bar (1.35 * 10 ⁸pa) pressure, but conventionally can exist up to 2000 bar (2 * 10 ⁸pa) or higher pressure.

Two limiting examples of this high-pressure fuel system are: common-rail injection system, wherein utilize high-pressure pump compressed fuel, and through being total to rail, be fed to Fuelinjection nozzle; And unit injection, it is combined into an assembly by high-pressure pump and Fuelinjection nozzle, reaches and surpasses 2000 bar (2 * 10 ⁸pa) the highest possibility spraying pressure.In two kinds of systems, when the described fuel of pressurization, fuel heating, reaches about 100 ℃ or above temperature conventionally.

In common rail system, fuel is under high pressure stored in middle part pressure accumulator rail or independent pressure accumulator, is then delivered to injector.Conventionally, some of fuel through heating turn back to the low-tension side of fuel system or turn back to fuel container.In unit injection, fuel compresses to produce high injection pressure in injector.This so improved the temperature of fuel.

In two kinds of systems, before spraying, fuel is present in injector body, at this because the heat from combustion chamber is further through heating.Temperature at the fuel of injector tip can be up to 250-350 ℃.

Therefore,, before spraying, fuel is at 1350 bar (1.35 * 10 ⁸pa) to surpassing 2000 bar (2 * 10 ⁸pressurized at the temperature of pressure Pa) and approximately 100 ℃-350 ℃, is recycled back in fuel system sometimes, therefore increases the time that fuel experiences these conditions.

The common problem of diesel engine is the fouling of injector, particularly injector body and injector nozzle.Fouling also can occur in fuel filter.When nozzle becomes by clogged with deposits from diesel-fuel, there is injector nozzle fouling.The fouling of fuel filter can to get back to fuel container relevant with fuel recycle.Settling increases with the deteriorated of fuel.Settling can be taked the form of the burnt shape resistates of carbon containing or viscosity or gummy residue.Diesel-fuel is heated higher, if be particularly heated under pressure, they become more and more unstable.The diesel engine therefore with high-pressure fuel system can cause the degradation of fuel increasing.

The problem of injector fouling can occur when using the diesel-fuel of any type.Yet some fuel can tend to cause fouling especially, or fouling can occur more quickly when using these fuel.For example, have been found that the fuel that comprises biofuel more easily produces injector fouling.The diesel-fuel that comprises metal object class also can cause the settling increasing.Metal object class can specially join in fuel in compositions of additives, or can be used as the existence of pollutent thing class.If become and dissolve or be dispersed in fuel from the metal object class of fuel dispensing system, automobile-used distribution system, vehicle fuel system, other metal ingredient and lubricating oil, will pollute.

Transition metal causes the settling, particularly copper and the zinc thing class that increase especially.These can, conventionally to exist from the high level to 50ppm of several ppb (ppb-), still believe that may cause the level of problem is 0.1-50ppm, for example 0.1-10ppm.

When injector becomes obstruction or partial blocking, the conveying of fuel is compared with poor efficiency, and fuel mixes with air is bad.This causes in time the loss of engine power, the exhaust gas emission of increase and bad fuel economy.

When the size in injector nozzle hole reduces, the relative effect that settling gathers becomes more remarkable.By simple calculations, the 5 μ m layers that are deposited in 500 μ m holes have reduced by 4% circulation area, yet the 5 identical μ m layers that are deposited in 200 μ m holes have reduced by 9.8% circulation area.

At present, nitrogenous washing agent can join in diesel-fuel to reduce coking.Typical nitrogenous washing agent is that the succinic acid derivative replacing by polyisobutene reacts those that form with polyalkylene polyamine.Yet, comprise that the engine of renewal of thinner injector nozzle is more responsive, and existing diesel fuel may be not suitable for using together with combining these new work engines compared with small nozzle hole.

The inventor has developed diesel fuel composition, and it,, when having the diesel engine of high-pressure fuel system, provides with the diesel fuel composition of prior art and compare augmented performance.

Provide to stop or reduce and in diesel engine, occur that sedimental diesel fuel composition is favourable.Can think that these fuel compositions carry out the function of " keeping clean ", their stop or suppress fouling.

Yet also expectation provides diesel fuel composition, the settling having formed in engine is cleaned in its help, the settling particularly having formed on injector.When this fuel composition burns in diesel engine, therefrom remove settling, therefore realize " the cleaning " to the engine of fouling.

As the character of " keeping clean ", the engine of " cleaning " fouling can provide significant advantage.For example, the good clean increase that can cause increased power and/or fuel economy.In addition, from engine, particularly from injector, remove settling, can make the increase of the interval time in necessary maintenance or before replacing injector, therefore reduce maintenance cost.

Although for above-mentioned reasons, settling on injector is to have the particular problem existing in the modern diesel engine of high-pressure fuel system, but expectation provides a kind of diesel fuel composition that effective detergency is also provided in older conventional diesel engine, makes the single-fuel that pump provides can be used for all types of engines.

Also expect that fuel composition reduces the fouling of vehicle fuel strainer.It can be used for providing and stops or suppress the composition that fuel filter settling occurs, that is the function of " keeping clean ", is provided.It can be used for providing from fuel filter settling removes existing sedimental composition, and " cleaning " function is provided.Can provide the composition of these two functions particularly useful.

Find before the applicant, the additive for example, being formed by the Mannich reaction (Mannich reaction) of aldehyde, amine and low molecular weight phenols (4-dodecylphenol) can be useful to the settling in minimizing modern diesel engines.Such additive is described in WO 2010/097624 and WO 2009/040584.Yet, when the applicant uses and uses before identical reactant ratio, while preparing additive by aldehyde, amine and the Mannich reaction with the substituent phenol of branched hydrocarbyl radical, find the poor-performing of described additive.

According to a first aspect of the invention, provide a kind of diesel fuel composition, its product that comprises the Mannich reaction between following is as additive:

(a) aldehyde;

(b) amine; With

(c) substituted phenol;

Wherein said phenol is replaced by least one branched hydrocarbyl radical with 200-3000 molecular weight; Wherein, in being used to form the described Mannich reaction of additive, component (a) is 2.2-1.01:1 with the mol ratio of component (b); Component (a) is 1.99-1.01:1 with the mol ratio of component (c), and component (b) is 1:1.01-1.99 with the mol ratio of component (c).

Any aldehyde can be used as the aldehyde component (a) of Mannich additive.Preferred described aldehyde component (a) is aliphatic aldehyde.Preferred described aldehyde has 1-10 carbon atom, preferably 1-6 carbon atom, more preferably 1-3 carbon atom.Most preferably described aldehyde is formaldehyde.

The amine component of Mannich additive (b) can be have the amino of at least one NH group or multiamino compound one of at least.Applicable aminocompound comprises uncle's monoamine or secondary monoamine, and it has the hydrocarbon substituent of 1-30 carbon atom, or the hydrocarbon substituent that has approximately 30 carbon atoms of 1-of hydroxyl replacement.

Amine component (b) is polyamines in preferred embodiments.

Polyamines can be selected from any compound that comprises two or more amidos.Preferably, polyamines is that (gathering) alkylene polyamine (refers to alkylene polyamine or polyalkylene polyamine; In each case, within diamines is included in the implication of " polyamines ").Preferably, polyamines is (gathering) alkylene polyamine, and wherein alkylidene group component has 1-6, preferably 1-4, most preferably 2-3 carbon atom.Most preferably described polyamines is (gathering) ethylidene polyamines (that is, ethylidene polyamines or poly-ethylidene polyamines).

Preferably, described polyamines has 2-15 nitrogen-atoms, preferably 2-10 nitrogen-atoms, more preferably 2-8 nitrogen-atoms.

Preferably, described polyamine component (b) comprises R ¹r ²nCHR ³cHR ⁴nR ⁵r ⁶part, wherein R ¹, R ², R ³, R ⁴, R ⁵and R ⁶each independently selected from hydrogen and optional substituted alkyl, thiazolinyl, alkynyl, aryl, alkylaryl or arylalkyl substituting group.

Therefore, the polyamine reactant for the preparation of Mannich reaction products of the present invention preferably includes optional substituted quadrol residue.

Preferred R ¹and R ²be one of at least hydrogen.Preferred R ¹and R ²both are hydrogen.

Preferred R ¹, R ², R ⁵and R ⁶at least two be hydrogen.

Preferred R ³and R ⁴be one of at least hydrogen.In some preferred embodiment, R ³and R ⁴each be hydrogen.In some embodiments, R ³for hydrogen R ⁴for alkyl, C for example ₁-C ₄alkyl, particularly methyl.

Preferably, R ⁵and R ⁶be one of at least optional substituted alkyl, thiazolinyl, alkynyl, aryl, alkylaryl or arylalkyl substituting group.

At R ¹, R ², R ³, R ⁴, R ⁵and R ⁶be not one of at least in the embodiment of hydrogen, each is independently selected from optional substituted alkyl, thiazolinyl, alkynyl, aryl, alkylaryl or arylalkyl part.Preferably, each is independently selected from hydrogen and optional substituted C (1-6) moieties.

In particularly preferred compound, R ¹, R ², R ³, R ⁴and R ⁵each be hydrogen and R ⁶for optional substituted alkyl, thiazolinyl, alkynyl, aryl, alkylaryl or arylalkyl substituting group.R preferably ⁶for optional substituted C (1-6) moieties.

Such moieties can be selected from following group and replaces with one or more: hydroxyl, amino (unsubstituted amino particularly;-NH-, NH ₂), sulfenyl, sulphur oxygen base, C (1-4) alkoxyl group, nitro, halogen (particularly chlorine or fluorine) and sulfydryl.

May have one or more heteroatomss to be bonded to alkyl chain, for example O, N or S, to provide ether, amine or thioether.

Particularly preferred substituent R ¹, R ², R ³, R ⁴, R ⁵or R ⁶for hydroxyl-C (1-4) alkyl and amino-(C (1-4) alkyl, particularly HO-CH ₂-CH ₂-and H ₂n-CH ₂-CH ₂-.

Compatibly, polyamines comprises only amine functionality, or amine and carbinol-functional degree.

Polyamines can for example be selected from following: quadrol, Diethylenetriamine, three second tetramines, tetraethylene-pentamine, five second hexamines, six second seven amine, seven second eight amine, propane-1,2-diamines, 2 (2-amino-ethylamino) ethanol and N', two (2-amino-ethyl) quadrol (N (CH of N'- ₂cH ₂nH ₂) ₃).Most preferably described polyamines comprises tetraethylene-pentamine or quadrol.

The mixture of isomer and/or oligopolymer is contained in commercially available polyamines source conventionally, and the product of being prepared by these commercially available mixtures falls within the scope of the invention.

The polyamines that is used to form Mannich additive of the present invention can be straight chain or branching, and can comprise ring texture.

Phenol component (c) for the preparation of Mannich additive of the present invention can be replaced (except described phenol OH) by 1-4 group on aromatic ring.For example it can be three replacements or dibasic phenol.Most preferred composition (c) is mono-substituted phenol.Replacement can be at ortho position and/or a position and/or contraposition.

Each phenol moieties can adjacent, or contraposition by aldehyde/amine residue, replaced.The most common formation wherein aldehyde residue is the compound of ortho position or para-orientation.May obtain the mixture of compound.In preferred embodiments, initial phenol is para-orientation, therefore obtains the product that ortho position replaces.

Phenol can be replaced by any common group, for example following one or more: alkyl, thiazolinyl, alkynyl, nitroxyl, carboxylic acid, ester, ether, alkoxyl group, halogen, other hydroxyl, sulfydryl, alkyl thiol, alkyl sulfide oxygen base, sulphur oxygen base, aryl, arylalkyl, replacement or unsubstituted amido or nitro.

As mentioned above, phenol comprises at least one branched hydrocarbyl radical substituting group.Hydrocarbyl substituent can optionally be replaced below: for example hydroxyl, halogen (particularly chlorine and fluorine), alkoxyl group, alkyl, sulfydryl, alkyl sulfide oxygen base, aryl or amino residue.Preferably, alkyl is comprised of carbon and hydrogen atom substantially.Substituted phenol can comprise the alkenyl or alkynyl residue that contains one or more pairs of keys and/or triple bond.

Substituting group based on alkyl is preferably mainly saturated, and for every 10 the carbon-to-carbon singly-bounds that exist, they comprise and are no more than a carbon-to-carbon unsaturated bond.Most preferably for every 50 C-Cs that exist, they comprise and are no more than a carbon-to-carbon unsaturated bond.

Preferably, component (c) is the monoalkyl phenol of monoalkyl phenol, particularly para-orientation, and wherein said substituent alkyl chain is branching.

In preferred embodiments, for the preparation of the phenol component (c) of Mannich reaction products additive (ii), comprise main or saturated branched hydrocarbyl radical substituting group fully.Preferably, this main or fully saturated hydrocarbyl substituent along the length branching of chain.Length branching along described chain refers to that it has many branches by leading (or the longest) chain.Preferably, along at least every 10 carbon atom You Yige branches of described main chain, preferably at least every 6 carbon, compatibly at least every 4 carbon, for example every 3 carbon atoms or every 2 carbon atoms.

Particular carbon atom in main hydrocarbyl chain (it is preferably alkene chain) can have one or two branch's alkyl.Branch's alkyl refers to that alkyl does not form the part of main chain but directly connects thereon.So can comprise-CHR of main hydrocarbyl chain ¹-or-CR ¹r ²-part, wherein R ¹and R ²for branch's alkyl.

Preferably, each branch's alkyl is alkyl, preferably C ₁-C ₄alkyl, for example propyl group, ethyl or most preferable.

In some preferred embodiment, for the preparation of the phenol component (c) of Mannich reaction products additive (ii), comprise hydrocarbyl substituent, by methyl, the main chain along them replaces for it.Compatibly, have a plurality of carbon atoms, its each there are two methyl substituents.

Preferably, tapping point is along the substantially first-class distance of alkyl main chain of phenol component (c).

Component (c) for the preparation of additive (ii) comprises at least one branched hydrocarbyl radical substituting group.Preferably this is alkyl substituent.In particularly preferred embodiments, hydrocarbyl substituent, derived from polyolefine, is suitably the polymkeric substance of branched olefin, for example polyisobutene or polypropylene.

In particularly preferred embodiments, the component (c) for the preparation of Mannich reaction products additive (ii) comprises poly-(iso-butylene) derivative substituting group.

Therefore, for described Mannich reaction products additive of the present invention, preferably include the hydrocarbyl chain with following repeating unit:

Poly-(iso-butylene) is by iso-butylene (CH ₃) ₂c=CH ₂addition polymerization preparation.Each molecule of the polymkeric substance obtaining comprises monoene part.

Conventional polyisobutene and be called as " hyperergy " polyisobutene and be applicable to prepare additive of the present invention (i).Highly reactive polyisobutenes is in the present context defined as following polyisobutene: wherein at least 50% of end olefinic double bond, preferably 70% or mostly more be the vinylidene type of describing as in EP 0565285.Particularly preferred polyisobutene is to have those that surpass 80 % by mole and maximum 100% terminal vinylidene, those as described in EP 1344785.

Other method of preparing the phenol (phenol that for example polyisobutene replaces) of polyalkylene replacement is well known by persons skilled in the art, and is included in the method for describing in EP 831141.

The hydrocarbyl substituent of component (c) has the molecular-weight average of 200-3000.Preferably, it has at least 225 molecular weight, and compatibly at least 250, preferably at least 275, compatibly at least 300, for example at least 325 or at least 350.In some embodiments, the hydrocarbyl substituent of component (c) has at least 375 molecular-weight average, and preferably at least 400, compatibly at least 475, for example at least 500.

In some embodiments, component (c) can comprise the hydrocarbyl substituent of the molecular-weight average with maximum 2800, preferably maximum 2600, for example maximum 2500 or maximum 2400.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 400-2500, for example 450-2400, preferably 500-1500, compatibly 550-1300.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 200-600.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 500-1000.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 700-1300.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 1000-2000.

In some embodiments, the hydrocarbyl substituent of component (c) has the molecular-weight average of 1700-2600, for example 2000-2500.

Except as otherwise noted, otherwise the whole molecular-weight average that relate to are herein number-average molecular weight.

For the preparation of the component (a) of Mannich product additive of the present invention, (b) and (c) mixture of inclusion compound and/or the mixture of isomer separately.

In order to form Mannich additive of the present invention, component (a) and (b) preferably by following mol ratio (aldehyde: amine) reaction: 2.2-1.1:1,2.2-1.2:1 preferably, more preferably 2.2-1.4:1,2.1-1.5:1 compatibly, preferably 2.05-1.55:1, preferably 2-1.6:1, compatibly 1.95-1.65:1, for example 1.9-1.7:1.

Component in reaction mixture (a) and component (b) (aldehyde: mol ratio amine) is 1.4:1 at least preferably.Compatibly be at least 1.5:1,1.6:1 at least, preferably at least 1.65:1, for example at least 1.7:1 or at least 1.75:1.

Preferably, component in reaction mixture (a) and component (b) (aldehyde: mol ratio amine) is maximum 2.2:1, preferred 2.1:1 at most, more preferably 2:1 at most, 1.95:1 at most compatibly, 1.9:1 at most for example, or 1.85:1 at most.

In order to form preferred Mannich additive of the present invention, component in reaction mixture (a) and component (c) (aldehyde: the preferred 1.95-1.05:1 of mol ratio phenol), preferred 1.9-1.05:1, more preferably 1.8-1.1:1,1.7-1.1:1 compatibly, preferably 165-1.15:1, more preferably 1.6-1.2:1, compatibly 1.55-1.25:1, for example, be 1.5-1.3:1.

Preferably, in the described reaction mixture for the preparation of Mannich additive of the present invention, component (a) and component (c) (aldehyde: mol ratio phenol) is 1:1 at least.Preferably be at least 1.1:1,1.15:1 at least compatibly, preferred 1.2:1 at least, more preferably 1.25:1 at least, for example 1.3:1 at least.

Preferably, component (a) and component (c) (aldehyde: mol ratio phenol) is maximum 1.8:1.Be preferably maximum 1.7:1; Preferred at most 1.65:1,1.6:1 at most compatibly, preferred 1.55:1 at most, for example 1.5:1 at most.

Compatibly, in the reaction mixture for the preparation of Mannich additive, component (b) and component (c) (amine: mol ratio phenol) is 1:1.05-1.95, preferred 1:1.05-1.9, more preferably 1:1.05-1.8, is suitably 1:1.1-1.7, be preferably 1:1.1-1.6, being suitably 1:1.15-1.5, being preferably 1:1.15-1.45, for example, is 1:1.2-1.4.

Component (c) and component (b) (phenol: mol ratio amine) mostly preferably is most 2:1.Can mostly be 1.9:1 most, compatibly mostly be most 1.8:1, preferably mostly be most 1.7:1, more preferably mostly be most 1.6:1, preferably mostly be most 1.5:1, for example, mostly be 1.45:1 or maximum 1.4:1 most.

Component (c) and component (b) (phenol: mol ratio amine) is 1:1 at least preferably.Can be at least 1.05:1,1.1:1 at least preferably, more preferably 1.15:1 at least, for example 1.2:1 at least.

In some preferred embodiments, in the reaction for the preparation of Mannich additive of the present invention, component (a) is 2-1.6:1 with the mol ratio of component (b), component (a) is 1.6-1.2:1 with the mol ratio of component (c), and component (b) is 1:1.1-1.5 with the mol ratio of component (c).

In some preferred embodiments, in the reaction for the preparation of Mannich additive of the present invention, component (a) is 1.9-1.7:1 with the mol ratio of component (b), component (a) is 1.5-1.3:1 with the mol ratio of component (c), and component (b) is 1:1.2-1.4 with the mol ratio of component (c).

In the described Mannich reaction for the preparation of additive of the present invention, component (a), (b) and mol ratio (c) are extremely important.The inventor found if the ratio using drops on beyond this scope, and described additive is so effective.

In some preferred embodiments, diesel fuel composition of the present invention can further comprise quaternary ammonium salt additive.Compatibly quaternary ammonium salt additive reacts by quaternizing agent and the acylating agent being replaced by alkyl and formula (B1) or amine (B2) the compound reaction forming and forms:

R wherein ²and R ³for the identical or different alkyl with 1-22 carbon atom, thiazolinyl or aryl; X is key or the alkylidene group with 1-20 carbon atom; N is 0-20; M is 1-5; And R ⁴for hydrogen or C ₁-C ₂₂alkyl.

Described quaternizing agent can compatibly be selected from ester and non-ester.

In some preferred embodiments, the quaternizing agent that is used to form described quaternary ammonium salt additive of the present invention is ester.Preferred ester quaternizing agent is formula RCOOR ¹compound, wherein R is optional substituted alkyl, thiazolinyl, aryl or alkylaryl and R ¹for C ₁-C ₂₂alkyl, aryl or alkylaryl.

Applicable ester quaternizing agent comprises having 3.5 or less pK _athe ester of carboxylic acid.

Formula RCOOR ¹compound be preferably the ester of the carboxylic acid that is selected from substituted aromatic carboxylic acid, alpha-hydroxy carboxylic acid compounds and polycarboxylic acid.

In some preferred embodiments, formula RCOOR ¹the compound ester that is substituted aromatic carboxylic acid, so R is substituted aryl.

Preferably R is the substituted aryl with 6-10 carbon atom, is preferably phenyl or naphthyl, most preferably phenyl.R is for compatibly by one or more carbalkoxy, nitro, cyano group, hydroxyl, SR of being selected from ⁵or NR ⁵r ⁶group replace.R ⁵and R ⁶each can be hydrogen or optional substituted alkyl, thiazolinyl, aryl or carbalkoxy.Preferred R ⁵and R ⁶each be hydrogen or optional substituted C ₁-C ₂₂alkyl, preferably hydrogen or C ₁-C ₁₆alkyl, preferably hydrogen or C ₁-C ₁₀alkyl, more preferably hydrogen C ₁-C ₄alkyl.Preferred R ⁵for hydrogen and R ⁶for hydrogen or C ₁-C ₄alkyl.R most preferably ⁵and R ⁶be both hydrogen.Preferably R is for being selected from hydroxyl, carbalkoxy, nitro, cyano group and NH ₂the aryl that replaces of one or more groups.R can be polysubstituted aryl, for example trihydroxy-phenyl.Preferably R is mono-substituted aryl.Preferably R is the aryl that ortho position replaces.Compatibly R is selected from OH, NH ₂, NO ₂or the group of COOMe replaces.Preferably R is by OH or NH ₂group replaces.Compatibly R is the aryl that hydroxyl replaces.Most preferably R is 2-hydroxyphenyl.

Preferred R ¹for alkyl or alkylaryl.R ¹can be C ₁-C ₁₆alkyl, preferably C ₁-C ₁₀alkyl, is suitably C ₁-C ₈alkyl.R ¹can be C ₁-C ₁₆alkylaryl, preferably C ₁-C ₁₀alkyl, is suitably C ₁-C ₈alkylaryl.R ¹can be methyl, ethyl, propyl group, butyl, amyl group, benzyl or their isomer.Preferred R ¹for benzyl or methyl.R most preferably ¹for methyl.

Formula RCOOR ¹particularly preferred compound be wintergreen oil.

In some embodiments, formula RCOOR ¹the compound ester that is alpha-hydroxy carboxylic acid compounds.In these embodiments, compound has following structure:

R wherein ⁷and R ⁸for identical or different and be selected from separately hydrogen, alkyl, thiazolinyl, aralkyl or aryl.The compound that is applicable to the type is herein described to some extent in EP 1254889.

Wherein RCOO is the formula RCOOR of alpha-hydroxy carboxylic acid compounds residue ¹the example of compound comprise methyl esters, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, benzyl ester, phenylester and the allyl ester of 2-hydroxy-iso-butyric acid; The methyl esters of 2-hydroxy-2-methyl butyric acid, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, benzyl ester, phenylester and allyl ester; The methyl esters of 2-hydroxyl-2 Ethylbutanoic acid, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, benzyl ester, phenylester and allyl ester; The methyl esters of lactic acid, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, benzyl ester, phenylester and allyl ester; Methyl esters, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, allyl ester, benzyl ester and phenylester with oxyacetic acid.Above, preferred compound is 2-hydroxy-methyl isobutyl acid.

In some embodiments, formula RCOOR ¹the compound ester that is polycarboxylic acid.This definition is intended to comprise dicarboxylic acid and the carboxylic acid having more than 2 acid moieties.In these embodiments, RCOO preferably exists with the form of ester, and one or more other acid groups that are present in radicals R are esterified form.Preferred ester is C ₁-C ₄alkyl ester.

Ester quaternizing agent can be selected from the diester of oxalic acid, the diester of the diester of phthalic acid, toxilic acid, the diester of the diester of propanedioic acid or citric acid.Formula RCOOR ¹a particularly preferred compound be dimethyl oxalate.

In preferred embodiments, formula RCOOR ¹compound be the pK having lower than 3.5 _athe ester of carboxylic acid.At compound, comprise in these embodiments of more than one acid groups, be intended to relate to the first dissociation constant.

Ester quaternizing agent can be selected from the ester of carboxylic acid, and described carboxylic acid is selected from the one or more of oxalic acid, phthalic acid, Whitfield's ointment, toxilic acid, propanedioic acid, citric acid, nitrobenzoic acid, benzaminic acid and 2,4,6-trihydroxybenzoic acid.

Preferred ester quaternizing agent comprises dimethyl oxalate, 2-nitrobenzene methyl and wintergreen oil.

The non-ester quaternizing agent being applicable to can comprise carbonate, the alkyl substituted epoxide with sour combination, alkylogen, alkylsulfonate, sultone, the phosphoric acid salt of alkyl replacement, borate, alkyl nitride, alkyl nitrate, oxyhydroxide, N-oxide compound or their mixture of alkyl replacement that dialkyl sulfate, benzyl halide, alkyl replace.

In some embodiments, quaternary ammonium salt can be by the preparation of for example alkyl or benzyl halide (particularly muriate), and then standing ion exchange reaction provides the different negatively charged ion part as quaternary ammonium salt.This method can be suitable for preparing quaternary ammonium hydroxide, alkoxide, nitrite or nitrate.

Preferred non-ester quaternizing agent comprises carbonate, the alkyl substituted epoxide with sour combination, alkylogen, alkylsulfonate, sultone, the phosphoric acid salt of alkyl replacement, borate, N-oxide compound or their mixture of alkyl replacement that dialkyl sulfate, benzyl halide, alkyl replace.

Be suitable for herein dialkyl sulfate as quaternizing agent and be included in alkyl chain and comprise thering is 1-10, preferably those of the alkyl of 1-4 carbon atom.Preferred compound is Dimethylsulfate.

Applicable benzyl halide comprises muriate, bromide and iodide.Phenyl can be optionally and is replaced by for example one or more alkyl or alkenyls, particularly when using muriate.Preferred compound is bromotoluene.

The carbonate that applicable alkyl replaces can comprise two alkyl that can be identical or different.Each alkyl can comprise 1-50 carbon atom, preferably 1-20 carbon atom, more preferably 1-10 carbon atom, compatibly 1-5 carbon atom.Preferably described or each alkyl is alkyl.The preferred compound of this type comprises diethyl carbonate and dimethyl carbonate.

The epoxide that applicable alkyl replaces has with following formula:

R wherein ¹, R ², R ³and R ⁴each independently for hydrogen or there is the alkyl of 1-50 carbon atom.The example of applicable epoxide comprises oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min. and oxidation stilbene.Alkyl epoxide is used as quaternizing agent with acid combination.The acylating agent replacing at alkyl is in the embodiment of dicarboxyl acylating agent, does not need to add independent acid.Yet in other embodiments, can use for example acid of acetic acid.

Particularly preferred epoxide quaternizing agent is propylene oxide and Styrene oxide 98min..

Be suitable for alkylogen herein and comprise muriate, bromide and iodide.

Applicable alkylsulfonate comprises having 1-20, preferably 1-10, and more preferably those of 1-4 carbon atom.

Applicable sultone comprises the third sultone and fourth sultone.

The phosphoric acid salt that applicable alkyl replaces comprises Acidic phosphates salt, trialkyl phosphoric acid salt and O, O-dialkyl dithiophosphate.Preferred alkyl has 1-12 carbon atom.

The borate group that applicable alkyl replaces comprises the alkyl borate with 1-12 carbon atom.

Preferred alkyl nitrite and alkyl nitrate have 1-12 carbon atom.

Preferably, non-ester quaternizing agent be selected from carbonate that dialkyl sulfate, benzyl halide, alkyl replace, with the alkyl substituted epoxide of sour combination and their mixture.

For particularly preferred non-ester quaternizing agent herein, it be the epoxide with the alkyl replacement of sour combination.These can comprise the sour embodiment that wherein provides independent, or the embodiment that wherein acid provides by just quaternized tertiary amine compound.Preferably, acid provides by just quaternized tertiary amine molecule.

For preferred quaternizing agent herein, comprise dimethyl oxalate, 2-nitrobenzene methyl, wintergreen oil and Styrene oxide 98min. or the propylene oxide of being optionally combined with other acid.

In order to form quaternary ammonium salt additive of the present invention, described quaternizing agent and the acylating agent being replaced by alkyl and formula (B1) or amine (B2) react the compound forming and react.

When the compound of use formula (B1), R ⁴be preferably hydrogen or C ₁-C ₁₆alkyl, preferably C ₁-C ₁₀alkyl, more preferably C ₁-C ₆alkyl.At R ⁴during for alkyl, it can be straight chain or branching.It can be replaced by for example hydroxyl or alkoxy substituent.Preferred R ⁴for non-substituted alkyl.Preferred R ⁴be selected from hydrogen, methyl, ethyl, propyl group, butyl and their isomer.R most preferably ⁴for hydrogen.

When the compound of use formula (B2), m is preferably 2 or 3, and most preferably 2; N is preferably 0-15, preferably 0-10, more preferably 0-5.Most preferably n be 0 and the compound of formula (B2) be alcohol.

The acylating agent that preferably alkyl replaces reacts with the diamine compound of formula (B1).

R ²and R ³for thering is identical or different alkyl, thiazolinyl or the aryl of 1-22 carbon atom.R in some embodiments ²and R ³can be joined together to form ring structure, for example piperidines or imidazoles part.R ²and R ³can be the alkyl or alkenyl of branching.Each can for example be replaced by hydroxyl or alkoxy substituent.

Preferred R ²and R ³be C independently of one another ₁-C ₁₆alkyl, preferred C ₁-C ₁₀alkyl.R ²and R ³can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group or these any isomer independently.Preferred R ²and R ³be C independently of one another ₁-C ₄alkyl.Preferred R ²for methyl.Preferred R ³for methyl.

X is key or the alkylidene group with 1-20 carbon atom.In preferred embodiments, when X alkylidene group, that this group can be straight chain or branching.Alkylidene group can comprise ring structure therein.It can for example optionally be replaced by hydroxyl or alkoxy substituent.

X is preferably the alkylidene group with 1-16 carbon atom, preferably 1-12 carbon atom, more preferably 1-8 carbon atom, for example 2-6 carbon atom or 2-5 carbon atom.Most preferably X is ethylidene, propylidene or butylidene, is in particular propylidene.

The example that is applicable to the compound of formula (B1) herein comprises: 1-amino piperidine, 1-(2-amino-ethyl) piperidines, 1-(3-aminopropyl)-pipecoline, 1-methyl-(4-methylamino-) piperidines, 4-(1-pyrrolidyl) piperidines, 1-(2-amino-ethyl) tetramethyleneimine, 2-(2-amino-ethyl)-1-crassitude, N, N-diethyl ethylenediamine, N, N-dimethyl-ethylenediamine, N, N-dibutyl quadrol, N, N-diethyl-l, 3-diaminopropanes, N, N dimethyl-1,3-diaminopropanes, N, N, N'-trimethylammonium quadrol, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methyl ethylenediamine, N, N, N'-triethyl quadrol, 3-dimethylamino propylamine, 3-diethyl amino propylamine, 3-dibutyl amino propyl amine, N, N, N'-trimethylammonium-1,3-propylene diamine, 1,3-propylene diamine, N, N, 2,2-tetramethyl--l, 3-propylene diamine, 2-amino-5-diethylamino pentane, N, N, N', N'-tetraethyl-Diethylenetriamine, 3,3'-diamino-N-methyl-di-n-propylamine, 3,3'-imino-two (N, N-dimethyl propylamine), 1-(3-aminopropyl) imidazoles and 4-(3-aminopropyl) morpholine, 1-(2-amino-ethyl) piperidines, 3,3-diamino-N-methyl-di-n-propylamine, 3,3-amino two (N, N-dimethyl propylamine) or their combinations.

In some preferred embodiments, the compound of formula (B1) is selected from N, N-dimethyl-1,3-diaminopropanes, N, N-diethyl-1,3-diaminopropanes, N, N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dibutyl quadrol or their combination.

The example that is applicable to formula (B2) compound herein comprises alkanolamine, include but not limited to trolamine, N, N-dimethylamino propyl alcohol, N, N-diethylamino propyl alcohol, N, N-diethylamino butanols, tri-isopropanolamine, 1-[2-hydroxyethyl] piperidines, 2-[2-(dimethylamine) oxyethyl group]-ethanol, N-ethyldiethanolamine, N methyldiethanol amine, N butyl diethanol amine, N, N-DEAE diethylaminoethanol, N, N-dimethylamino-ethanol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol.

In some preferred embodiments, the compound of formula (B2) is selected from tri-isopropanolamine, 1-[2-hydroxyethyl] piperidines, 2-[2-(dimethylamine) oxyethyl group]-ethanol, N-ethyldiethanolamine, N methyldiethanol amine, N butyl diethanol amine, N, N-DEAE diethylaminoethanol, N, N-dimethylaminoethanol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol or their combination.

The particularly preferred compound of formula (B1) is dimethylamino propylamine.

The acylation reaction that formula (B1) or amine (B2) and alkyl replace.Monocarboxylic acid, di-carboxylic acid or the polycarboxylic acid that the acylating agent that alkyl replaces can replace based on alkyl or their reactive equivalent.The acylating agent that preferably alkyl replaces is the succinic acid compound that alkyl replaces, for example succsinic acid or succinyl oxide.

Hydrocarbyl substituent preferably comprises at least 10, and more preferably at least 12,30 or 50 carbon atoms for example.It can comprise approximately 200 carbon atoms at most.Preferably hydrocarbyl substituent has the number-average molecular weight (Mn) of 170-2800,250-1500 for example, preferably 500-1500 and more preferably 500-1100.The Mn of 700-1300 is particularly preferred.

Substituting group based on alkyl can for example, by having the monoolefine of 2-10 carbon atom and homopolymer or the interpretation (multipolymer, ter-polymers) of diolefine (such as ethene, propylene, butane-1, iso-butylene, divinyl, isoprene, 1-hexene, 1-octene etc.) are made.Preferably these alkene are 1-monoolefine.Hydrocarbyl substituent also can for example, derived from halogenation (chlorination or the bromination) analogue of such homopolymer or interpretation.Or substituting group can be made by other sources, for example monomer high molecular weight olefin (for example 1-40 alkene) and their chlorination analogue and hydrochlorinate analogue; Aliphatic series petroleum fractions, for example paraffin and their cracking and chlorination analogue and hydrochlorinate analogue, white oil; The synthetic alkene of for example producing by Z-N method (for example poly-(ethene) fat); And other source well known by persons skilled in the art.If expectation, degree of unsaturation any in substituting group can reduce or eliminate by the hydrogenization according to program known in the art.

Term used herein " alkyl " represents to have the carbon atom of the remainder that is directly attached to molecule and have the group that is mainly aliphatic hydrocrbon characteristic.The group based on alkyl being applicable to can contain nonhydrocarbon part.For example, for every 10 carbon atoms, they can contain maximum non-alkyl, as long as this non-hydroxyl does not significantly change the main hydrocarbon characteristic of described group.Those skilled in the art should be familiar with such group, and it comprises such as hydroxyl, oxygen, halogen (particularly chlorine and fluorine), alkoxyl group, alkyl thiol, alkyl sulfide oxygen base etc.The preferred substituting group based on alkyl is pure aliphatic hydrocrbon characteristic and does not contain above-mentioned group.

Poly-(iso-butylene) that the preferred substituting group based on alkyl is known in the art.Therefore, in particularly preferred embodiments, the acylating agent that alkyl replaces is the succinyl oxide that polyisobutenyl replaces.

Being prepared as of the succinyl oxide (PIBSA) that polyisobutenyl replaces is proven in this area.Applicable method comprise by polyisobutene and maleic anhydride thermal response (referring to example US-A-3,361,673 and US-A-3,018,250), with by halogenation, particularly the polyisobutene of chlorination (PIB) reacts (referring to example US-A-3,172,892) with maleic anhydride.Or polyisobutenyl succinic anhydride can be by mixing polyolefine and chlorine being prepared to (referring to example GB-A-949,981) by mixture with maleic anhydride.

Conventional polyisobutene and so-called " hyperergy " polyisobutene are applicable to prepare additive of the present invention (i).Highly reactive polyisobutenes is in the present context defined as following polyisobutene: wherein at least 50% of end olefinic double bond, preferably 70% or mostly more be the vinylidene type of describing as in EP 0565285.Particularly preferred polyisobutene is to have those that surpass 80 % by mole and maximum 100% terminal vinylidene, those as described in EP 1344785.

Other preferred alkyl comprises for example having to have those of internal olefin as what describe in the disclosed application of applicant WO 2007/015080.

Internal olefin used herein refers to mainly contain any alkene of the two keys of non-α, i.e. β or higher alkene.Preferably such material is entirely β or higher alkene substantially, for example, comprise the alpha-olefin that is less than 10 % by weight, is more preferably less than 5 % by weight or is less than 2 % by weight.Typical internal olefin comprises Neodene 1518 IO that can derive from Shell.

Internal olefin is called as isomerized alkene sometimes, and can by isomerization method known in the art, be prepared by alpha-olefin, maybe can derive from other sources.The fact that they are also referred to as internal olefin has reflected that they are not necessarily prepared by isomerization.

Some preferred acylating agent for the preparation of quaternary ammonium salt additive of the present invention is succsinic acid or the succinyl oxide that polyisobutene replaces.When the compound of formula (B2) reacts with succinic acylating agent, the product obtaining is succinate.As succinic acylating agent and R wherein ⁴during for the compound reaction of the formula (B1) of hydrogen, the product obtaining can be succinimide or succinic diamide.As succinic acylating agent and R wherein ⁴be not compound when reaction of the formula (B1) of hydrogen, the product obtaining is acid amides.

In preferred embodiments, the acylating agent that alkyl replaces and the reaction product of formula (B1) or amine (B2) are acid amides or ester.

In preferred embodiments, the acylating agent that alkyl replaces and the reaction product of formula (B1) or amine (B2) also have at least one remaining hydroxy-acid group.This can realize by following: select to there is binary or polycarboxylic acid or their reactive equivalent, and the applicable mol ratio of selecting type (B1) or amine (B2).By R wherein ⁴in the situation of the acid amides of preparing for the amine of the formula (B2) of hydrogen, also may must control reaction conditions to avoid forming imide.Such technology is in those of ordinary skills' limit of power.

For avoidance of doubt, succinate comprises having general formula (C ₁) monoester compound and there is general formula (C ₂) diester compound; Succinimide has general formula (C ₃); And succinic diamide comprises having general formula (C ₄) monomer amide compounds and there is general formula (C ₅) diamide compound:

In particularly preferred embodiments, the tertiary ammonium salt that quaternary ammonium salt additive of the present invention is prepared for the succinyl oxide being replaced by dimethylamino propylamine and polyisobutene.The substituent molecular-weight average of polyisobutene is preferably 700-1300, more preferably 900-1100.

Particularly preferred quaternary ammonium salt of the present invention is polyisobutenyl succinic acylating agent and dimethylamino propylamine (N; N dimethyl 1; 3 propylene diamine) form imide; then use wintergreen oil quaternized; or form half amide, half acid, then use the quaternised reaction product of propylene oxide.

Quaternary ammonium salt additive of the present invention can be prepared by any applicable method.Such method is well known by persons skilled in the art and illustrates at this.Conventionally, quaternary ammonium salt additive is by preparing the heating of quaternizing agent and following compound: the acylating agent that described compound is replaced by alkyl and formula (B1) or amine (B2) optionally react preparation with the mol ratio of about 1:1 in the presence of solvent.The crude product mixture obtaining can directly be added in diesel-fuel, optionally after removing solvent.Still be present in any by product in mixture or remaining raw material not yet discovery can cause any infringement to Additive Properties.Therefore, the present invention can provide a kind of diesel fuel composition, the reaction product that it comprises quaternizing agent and the acylating agent of alkyl replacement and the reaction product of formula (B1) or amine (B2).

The applicable processing ratio of Mannich additive and quaternary ammonium salt additive (when existing) depends on the performance of expectation and uses therein the type of their engine.For example can need the additive of different levels to realize the performance of different levels.

Compatibly, in use, Mannich additive exists by following amount in diesel fuel composition: 1-10000ppm, preferably 1-1000ppm, more preferably 5-500ppm, compatibly 5-250ppm, for example 5-150ppm.

Compatibly, quaternary ammonium salt additive exists by following amount in diesel fuel composition: 1-10000ppm, preferably 1-1000ppm, more preferably 5-500ppm, compatibly 5-250ppm, for example 5-150ppm.

The weight ratio of quaternary ammonium salt additive and Mannich additive is preferably 1:10-10:1.Preferred 1:4-4:1, for example 1:3-3:1.

As previously mentioned, the known fuel that contains biofuel or metal can cause fouling.Harsh fuel, for example, contain those of high-level metal and/or high-level biofuel, compared with more not harsh fuel, can need the treatment rate of higher quaternary ammonium salt additive and/or Mannich additive.

Diesel fuel composition of the present invention can comprise one or more other additives, those that for example conventionally exist in diesel-fuel.These comprise for example antioxidant, dispersion agent, washing agent, metal deactivating compound, anti-settling agent, cold flow improver, cetane number improver, de-misting agent, stablizer, demulsifying compound, defoamer, inhibiter, improver for lubricating performance, dyestuff, marker, ignition dope, metal passivator, odor masking agent, flow improver and electroconductibility improving agent.In these additive types, the example of the suitable amount of each is well known by persons skilled in the art.

In some preferred embodiments, composition comprises the washing agent type that the derivative acylating agent of succsinic acid that polyisobutene replaces and the reaction of poly-ethylidene polyamines form in addition.Applicable compound is for example in WO 2009/040583, to describe.

Diesel-fuel comprises any fuel of the diesel engine that is applicable to pavement usage or non-pavement usage.This includes but not limited to be described as the fuel of diesel oil, navigation diesel oil, heavy fuel oil (HFO), industrial fuel wet goods.

Diesel fuel composition of the present invention can comprise the oil fuel based on oil, particularly intermediate distillate fuel oil.Such distillate fuel oil seethes with excitement conventionally within the scope of 110 ℃-500 ℃, for example 150 ℃-400 ℃.Diesel-fuel can comprise normal pressure cut or vacuum cut, pressure gasoline, or the mixture of any ratio of straight run and refinery streams (for example cut of heat and/or catalytic pyrolysis and hydrocracking).

Diesel fuel composition of the present invention can comprise Fischer-Tropsch fuel (Fischer Tropsch fuel).It can comprise non-renewable Fischer-Tropsch fuel, for example, be described as GTL (gas is to liquid) fuel, those of CTL (coal is to liquid) fuel and OTL (oil-sand is to liquid).

Diesel fuel composition of the present invention can comprise recyclable fuel, biological example fuel composition or biodiesel composition.

Diesel fuel composition can comprise first-generation biofuel.First-generation biofuel comprises vegetables oil for example, animal tallow and with the ester of the cooking fat of crossing.The biofuel of this form can obtain by oil and the transesterify of alcohol (monohydroxy-alcohol conventionally) under catalyzer exists, described oil for example, rapeseed oil, soya-bean oil, Thistle oil, palm 25 oil, Semen Maydis oil, peanut oil, Oleum Gossypii semen, butter, cocounut oil, physic-nut oil (Jatropha), wunflower seed oil, the cooking oil of using, hydrogenated vegetable oil or their any mixture.

Diesel fuel composition can comprise s-generation biofuel.S-generation biofuel is derived from renewable resources, and for example vegetables oil and animal tallow treated, in the refinery that is everlasting, often used hydrotreatment, the H-Bio method of for example being developed by Petrobras.S-generation biofuel can be similar to oil fuel based on oil stream in character and quality, such as from productions such as vegetables oil, animal tallows, and by ConocoPhillips press that Renewable Diesel sells and by Neste by the renewable diesel of NExBTL sale.

Diesel fuel composition of the present invention can comprise third generation biofuel.The utilization gasification of third generation biofuel and fischer-tropsch technologies, comprise those that are described as BTL (biomass are to liquid) fuel.Third generation biofuel and some s-generation biofuel do not have very big-difference, but are intended to utilize whole plant (biomass), have therefore widened raw material basis.

Diesel fuel composition can comprise any or all of mixture of above diesel fuel composition.

In some embodiments, diesel-fuel comprises Fischer-Tropsch fuel and/or biofuel.

In some embodiments, diesel fuel composition of the present invention can be the mixed diesel oil fuel that comprises biofuel.In such mixture, biofuel can exist by following amount: for example maximum 0.5%, maximum 1, maximum 2%, maximum 3%, maximum 4%, maximum 5%, maximum 10%, maximum 20%, maximum 30%, maximum 40%, maximum 50%, maximum 60%, maximum 70%, maximum 80%, maximum 90%, maximum 95% or maximum 99%.

In some embodiments, diesel fuel composition can comprise the second fuel, for example ethanol.Yet preferably, diesel fuel composition does not comprise ethanol.

Diesel fuel composition of the present invention can comprise relatively high sulphur content, for example, be greater than 0.05 % by weight, and for example 0.1% or 0.2%.

Yet in preferred embodiments, diesel-fuel has the sulphur content of maximum 0.05 % by weight, more preferably maximum 0.035 % by weight, particularly maximum 0.015%.The fuel with even lower level sulphur is also applicable to, and for example, has the fuel that is less than 50ppm sulphur weight, is preferably less than 20ppm, for example 10ppm or lower.

When existing, wrap metallic thing class and exist usually used as pollutent, for example, by being present in fuel or the corrosion to metal and metal oxide surface from the acid class of lubricating oil.In use, fuel for example diesel-fuel touches metallic surface conventionally, such as among vehicle fuel system, fuel container, fuel transport equipment etc.Conventionally, wrap metallic pollutent and can comprise transition metal, for example zinc, iron and copper; I Zu Huo II family metal, for example sodium; For example plumbous with other metal.

Except can being present in the metallic pollutent of bag in diesel-fuel, can deliberately add the metallic thing class of bag to situation in fuel in addition.For example, as known in the art, can add the metallic fuel addition type catalyzer thing class of bag to help the regeneration of grain catcher.Such catalyzer is conventionally based on as mixture or independent metal, for example iron, cerium, I Zu He II family metal (for example calcium and strontium).Also use platinum and manganese.When fuel is used for having the diesel engine of high-pressure fuel system, the existence of such catalyzer also can cause injector deposits.

Wrap metallic pollutent, depend on its source, can be the form of insoluble particle or soluble compound or complex compound.Wrap metallic fuel addition type catalyzer and be generally soluble compound or complex compound or colloid thing class.

In some embodiments, wrap metallic thing class and comprise fuel addition type catalyzer.

In some embodiments, wrap metallic thing class and comprise zinc.

In a preferred embodiment, diesel fuel composition of the present invention comprises fuel addition type catalyzer, and it comprises and is selected from following metal: iron, cerium, I Zu He II family metal, platinum, manganese and their mixture.Preferably I Zu He II family metal comprises calcium and strontium.

Conventionally, wrapping the amount of metallic thing class in diesel-fuel, according to the gross weight of the metal in thing class, represent, is 0.1-50ppm weight, 0.1-10ppm weight for example, the weight based on diesel-fuel.

Compare with the diesel-fuel of prior art, when having the diesel engine of high-pressure fuel system, fuel composition of the present invention has shown improved performance.

According to a second aspect of the invention, provide additive-package, it provides the composition of first aspect after adding diesel-fuel to.

Additive-package can comprise Mannich additive, optional quaternary ammonium salt additive and the optional mixture of other additive (for example described above those).Or additive-package can comprise the solution of additive, compatibly in the mixture of hydrocarbon flux, for example aliphatic series and/or aromatic solvent; And/or oxidation solvent for example alcohol and/or ether.

According to a third aspect of the invention we, provide the method for operating diesel machine, described method is included in the composition of the first aspect of burning in engine.

According to a forth aspect of the invention, provide Mannich reaction products additive as defined in the first aspect about diesel fuel composition in order to improve the purposes of the motor performance of diesel engine as described in using during diesel fuel composition.

The preferred feature of second, third and fourth aspect limits as about first aspect.

The raising of performance can be by reducing or preventing settling in diesel engine to form to realize.This can think the raising of " keeping clean " performance.Therefore, it is a kind of by the composition of the first aspect of burning in described engine that the present invention can provide, and reduces or stop the method for settling formation in diesel engine.

The raising of performance can be by removing existing settling in diesel engine to realize.This can think the raising of " cleaning " performance.Therefore, it is a kind of by the composition of the first aspect of burning in described engine that the present invention can provide, and removes sedimental method from diesel engine.

In particularly preferred embodiments, the composition of a first aspect of the present invention can be used for providing the raising in " keeping clean " and " cleaning " performance.

In some preferred embodiments, the purposes of the third aspect can relate to uses quaternary ammonium salt additive in diesel fuel composition, optional and Mannich additive combination, to improve the motor performance of diesel engine when using described diesel fuel composition, wherein said diesel engine has high-pressure fuel system.

The feature with the modern diesel engine of high-pressure fuel system can be many modes.Such engine is equipped with the fuel injector with a plurality of holes conventionally, and each hole has import and outlet.

Such modern diesel engine feature can be gradually thin hole, and it makes the inlet diameter of jet hole be greater than exit diameter.

Such Modern Engine feature can be to have the hole of following exit diameter: be less than 500 μ m, be preferably less than 200 μ m, be more preferably less than 150 μ m, be preferably less than 100 μ m, be most preferably less than 80 μ m or less.

Such modern diesel engine feature can be that wherein said entrance inner edge is through the hole of full circle.

Such modern diesel engine feature can be to have the injector in more than one hole, compatibly more than 2 holes, and preferably more than 4 holes, for example 6 or more hole.

Such modern diesel engine feature can be to surpass the operational tip temperature of 250 ℃.

Such modern diesel engine feature can be to be greater than the fuel pressure of 1350 bar, is preferably greater than 1500 bar, more preferably greater than 2000 bar.

Purposes of the present invention preferably improves the performance of the engine with one or more above-mentioned features.

The present invention is particularly useful in and stops or reduce or remove the settling on engine spray device, and described engine operates under high pressure and high temperature, and wherein fuel can recirculation, and described engine comprises a plurality of pores, through described pore, fuel is transported to engine.The present invention is applicable to heavy vehicle and passenger vehicle engine used.Combine the direct passenger vehicle that sprays (or HSDI) engine at a high speed and can for example benefit from the present invention.

Within the injector body of modern diesel engine with high-pressure fuel system, between moving parts, may there is the only interval of 1-2 μ m, existing by the bond report of the engine problem that particularly injector bonding opening causes of injector in the art.Sedimental control in this region can be very important.

When the diesel engine for traditional, diesel fuel composition of the present invention also can provide augmented performance.Preferably, while using described composition while using described diesel fuel composition in thering is the modern diesel engine of high-pressure fuel system and in traditional diesel engine, realize augmented performance.This is important, because it allows to provide and can be used for new work engine and compared with the single-fuel of old vehicle.

The raising of the performance of diesel engine system can be measured by many methods.Applicable method depends on the type of engine and whether measures " keeping clean " and/or " cleaning " performance.

One of method of the raising of measurability energy is the power loss in testing by measurement controlled engine.The raising that " keeps cleaning " performance can reduce to measure by observing the power loss that compare with basic fuel finding." cleaning " performance can observe by the increased power when diesel fuel composition of the present invention is used for the engine of fouling.

The performance with the diesel engine of high-pressure fuel system improves and can measure by the raising of fuel economy.

The purposes of the third aspect is for also improving by the settling in minimizing, prevention or removal vehicle fuel strainer the performance of engine.

Sedimental level in vehicle fuel strainer can quantitatively or qualitatively be measured.In some cases, this only can be by checking that when removing strainer strainer measures.In other cases, sedimental level can be assessed during use.

Many vehicles are provided with fuel filter, and visual inspection strainer during use, to determine the level of buildup of solids and the needs that strainer is replaced.For example, a kind of such system is used the filter canister in transparent outer cover, the fuel level in its permission observation strainer, strainer and the degree of filter blocks.

Be not that fuel composition of the present invention is compared, use fuel composition of the present invention can cause the settling level in described fuel filter to reduce significantly.This allows the change frequency of strainer much lower and can guarantee that fuel filter did not lose efficacy during operation.Therefore, the use of composition of the present invention can cause the maintenance cost reducing.

In some embodiments, can suppress or reduce sedimental appearance in fuel filter.Therefore, can be observed " keeping clean " performance.In some embodiments, can remove existing settling from fuel filter.Therefore, can be observed " cleaning " performance.

The raising of performance also can use fuel composition of the present invention that the degree that on engine spray device, sedimental amount reduces is evaluated by consideration.For " keeping clean " performance, will observe settling and occur reducing.For " cleaning " performance, will observe existing sedimental removal.

Conventionally the direct measurement of not taking settling to gather, but infer from power loss or through the fuel flow of injector.

The purposes of the third aspect can improve by minimizing, prevention or the settling that comprise glue and paint of removal within injector body the performance of engine.

In Europe, for (the Co-ordinating European Council of CEC developing is made in the performance test of transport fuel, lubricant and other fluid, the industrial community that is called as CEC), developed a kind of new test, whether CEC F-98-08 by name, be suitable for using in meeting the new European Union discharge regulations engine of (being called " Europe 5 " regulations) to evaluate diesel-fuel.Peugeot DW 10 engines of described test based on using Europe 5 injectors, hereinafter referred to as DW 10 tests.It will further describe (seeing embodiment 4) in the context of embodiment.

Preferably, use fuel composition of the present invention to cause the settling reducing in DW 10 tests.For " keeping clean " performance, preferably observe the minimizing that settling occurs.For " cleaning " performance, preferably observe sedimental removal.DW 10 tests are for measuring in the power loss with the modern diesel engine of high-pressure fuel system.

For older engine, use the raising of XUD 9 test measurabilities energy.This test 9 is described in conjunction with the embodiments.

Compatibly, the use of fuel composition of the present invention can provide " keeping clean " performance in modern diesel engine, can suppress or prevent sedimental formation on the injector of these engines.Preferably, this performance makes to observe power loss after 32 hours and is less than 5%, is preferably less than 2%, by DW 10 thermometricallies.

Compatibly, the use of fuel composition of the present invention can provide " cleaning " performance in modern diesel engine, can remove the settling on the injector of the engine of fouling.Preferably, this performance made within 32 hours, within the power of the engine of fouling can turn back to the level disparity 1% reaching when using clean injector, in DW 10 tests, measured.

Preferably can realize " cleaning " rapidly, wherein power within 10 hours, turn back to use the viewed level disparity 1% of clean injector within, preferably within 8 hours, compatibly within 6 hours, preferably within 4 hours, more preferably within 2 hours.

Clean injector can comprise new-type injector or remove and for example clean injector of physics in ultra sonic bath.

Compatibly, performance that fuel composition of the present invention is used can be provided in conventional diesel engine " keeping clean ", can suppress or prevent sedimental formation on the injector of these engines.Preferably this performance makes to observe loss of flow after 10 hours and is less than 50%, is preferably less than 30%, by XUD-9 thermometrically.

Compatibly, the use of fuel composition of the present invention can provide " cleaning " performance in conventional diesel engine, can remove the settling on the injector of the engine of fouling.Preferably, this performance makes the flow of the engine loss of fouling within 10 hours, to improve 10% or more, in XUD-9 test, measures.

Any feature of any aspect of the present invention can suitably combine with any other feature.

With reference now to following non-limiting example, further set forth the present invention.

embodiment 1

The phenol that polyisobutene replaces is prepared as follows:

The polyisobutene (450.3g, 0.53 mole, 1 equivalent) with 750 molecular-weight average is heated to 45-50 ℃, then adds phenol (150.0g, 1.59 moles, 3 equivalents).Muddy mixture stirred and through approximately two hours, add boron trifluoride two etherates (15.0g, 0.10 mole, 0.18 equivalent) by 2-3ml aliquots containig, so that the orange liquid of clarification to be provided, it being stirred 5 hours at 45-50 ℃.Then add ammoniacal liquor 35% (10.5g, 0.22 mole) and reaction mixture is stirred 30 minutes.Vacuum distilling provides the cut of 81.3g.This stirs 5 minutes at 70 ℃ in toluene (250.3g), then adds the water of 250.4g.Layer is separated and toluene extract is washed with water more than twice.Remaining water and toluene go down divided by product is provided in vacuum, are the light yellow liquid (510.9g) of viscosity, the phenol content that it has the toluene level of 2 % by weight and is less than 0.2 % by weight.

This product is used for being prepared as follows additive A, i.e. Mannich additive of the present invention:

PIB 750 phenol (447.8g, 425.4g " activity " PIB phenol, 0.50 mole, 1.3 equivalents) with the remaining PIB content of 5 % by weight mix with quadrol (25.3g, 0.38 mole, 1 equivalent) and Caromax 20 solvents (225.6g).Uniform mixture is heated to 90-95 ℃.Then 36.7% formalin (57.12g, 0.69 mole, 1.8 equivalents) was added through 1 hour, then reaction mixture is remained on 95 ℃ 1 hour.Use Dean-Stark equipment to remove water.In distillation, collect afterwards the product of 708.3g.

embodiment 2(contrast)

Use is similar to the method that embodiment 1 describes, and the component mol ratio that use table 1 describes in detail is prepared non-contrast Mannich reaction products of the present invention.

Table 1

embodiment 3

By preparing below diesel fuel composition: additive is added in the aliquots containig of all taking from RF 06 basic fuel of common batch and comprising 1ppm zinc (as zinc neodecanoate).In all cases, use 75ppm as described and the crude product additive prepared in embodiment 1 and 2.

Following table 2 has shown the specification of RF 06 basic fuel.

Table 2

embodiment 4

The performance of diesel fuel composition of the present invention in modern diesel engine can be according to CECF-98-08 DW 10 method tests.

Injector engine fouling test is PSA DW10BTED4.Generally speaking, engine performance is:

Design: in-line four cylinder, overhead camshaft, uses EGR turbo-charging

Capacity: 1998cm ³

Combustion chamber: four valves, cavity piston (bowl in piston), the straight spray of wall guiding

Power: 100kW, 4000rpm

Moment of torsion: 320Nm, 2000rpm

Injection system: the common rail 6 hole injectors that use piezoelectricity to control.

Peak pressure: 1600 bar (1.6 * 10 ⁸pa).The proprietary design of SIEMENS VDO

Discharge is controlled: when combining with exhausted gas post-processing system (DPF), meet Europe IV limit value.

Select this engine as the design liaison of modern European high speed DID engine that can meet the present and the future's European Emission thing demand.Common-rail injection system is used has the ingress edge of full circle and the design of the high efficiency nozzle in conic jet hole, for best hydraulic flow.This class nozzle, when with high fuel pressure combination, allows to realize and improving aspect the noise of efficiency of combustion, reduction and the fuel consumption of reduction, but on disturbing the impact of fuel flow responsive, for example the settling in jet hole forms.These sedimental existence cause the thick discharge of remarkable loss and the increase of engine power.

Described test moves by the following injector designs that has represented the Europe V injector technology of expection.

Think and before starting fouling test, need to set up the reliable baseline of injector condition, therefore trial run plans in 16 hours of regulation test injector, are used non-fouling reference fuel.

The full details of CEC F-98-08 testing method can obtain from CEC.Coking circulation is summarized as follows.

1. according to the warm-up cycle of following progress (12 minutes):

Step	Time length (minute)	Engine speed (rpm)	Moment of torsion (Nm)
				1	2	Idle running	<5
2	3	2000	50
				3	4	3500	75
4	3	4000	100

2. the engine of 8 hours operation, repeats to form by 8 times that circulate below

3. in 60 seconds, be cooled to idle running, and dally 10 seconds

4. the warm-up period of 4 hours (soak period)

Standard C EC F-98-08 testing method is comprised of engine operation in 32 hours, repeats for 4 times of corresponding above step 1-3, and 3 repetitions of step 4.Except preheating and cooling 56 hours total testing times.

embodiment 5

According to the diesel fuel composition of embodiment 3 preparations, according to the DW-10 testing method of embodiment 4, test.

In all cases, use new injector and be wherein added with 1ppmZn (as neodecanoate) and the RF-06 basic fuel of 75ppm crude product additive moves circulation in 32 hours.Record is in all cases through the power loss of 32 hour test period.Result is presented at Fig. 1-6.

embodiment 6

The reaction product of the acylating agent that alkyl replaces and the compound of formula (B1) is prepared as follows:

523.88g (0.425 mole) PIBSA (being prepared by 1000MW PIB and maleic anhydride) and 373.02g Caromax 20 are packed in the container of 1 liter.Mixture is stirred under nitrogen and be heated to 50 ℃.Add 43.69g (0.425 mole) dimethylamino propylamine and mixture is heated to 160 ℃ of experience 5 hours, use Dean-Stark equipment to dewater simultaneously.

embodiment 7

Additive G(quaternary ammonium salt additive) be prepared as follows:

33.9kg (27.3 moles) is there is to the succinyl oxide that the poly-isobutyl-of 1000 PIB molecular weight replaces and be heated to 90 ℃.Add the dimethylamino propylamine of 2.79kg (27.3 moles) and mixture is stirred 1 hour at 90-100 ℃.Temperature is increased to 140 ℃ of experience 3 hours, dewaters simultaneously.Add the 2-Ethylhexyl Alcohol of 25kg, then add the wintergreen oil (27.3 moles) of 4.15kg, and mixture is kept 9.5 hours at 140 ℃.

embodiment 8

Diesel fuel composition is by following preparation: the crude product material (additive A) that 107.5ppm is obtained in embodiment 1 and 107.5ppm, add in the RF06 basic fuel that meets the specification that above table 2 (embodiment 3) provides together with the 1ppm zinc as zinc neodecanoate at the crude product material (additive G) of embodiment 7 acquisitions.This fuel composition is according to CECF-98-08DW 10 method tests, as described in Example 4.

In this case, first RF-06 basic fuel that recycles new injector for 32 hours and wherein added 1ppm Zn (as neodecanoate) moves.Due to the fouling of injector, this causes the power loss of certain level.

Then, second circulation in 32 hours moved as " cleaning " stage.The injector that the dirt that derives from the first stage is dirty is retained in engine, and is wherein to have added the RF-06 basic fuel of 1ppm Zn (as neodecanoate), 107.5ppm additive A and 107.5ppm additive G using the change of fuel

Test result is presented in Fig. 7.

embodiment 9

The validity of additive of the present invention can be evaluated for No. F-23-A-01 by test by standard industry-CEC testing method CEC in older engine type.

The coking of Peugeot XUD 9A/L engine measuring injector nozzle is used in this test, and the means of the injector nozzle coking tendency of distinguishing different between fuel are provided.Nozzle coking is between injector needle-valve and needle seating, to form the result of carbon deposits.The deposition of carbon deposits is because injector needle-valve and seat are exposed to burning gas, causes potentially the less desirable variation of motor performance.

Peugeot XUD 9A/L engine is 4 cylinder direct injection diesel engine of 1.9 liter capacities, derives from Peugeot Citroen Motors, is used in particular for CEC PF023 method.

This test engine is provided with clean injector, uses irregular injector needle-valve.Air flow quantity in different needle lift positions was measured before test on flow tester.Engine is operated under cycling condition to the time period of 10 hours.

Stage	Time (second)	Speed (rpm)	Moment of torsion (Nm)
				1	30	1200 ± 30	10 ± 2
2	60	3000 ± 30	50 ± 2
				3	60	1300 ± 30	35 ± 2
4	120	1850 ± 30	50 ± 2

Fuel promotes to form sedimental tendency on fuel injector by measure again injector nozzle air flow quantity when test finishes, and by those of these numerical value and test in the past to recently determining.According to whole nozzles, the air flow quantity reduction percentage in different needle lift positions recently represents result.Whole four nozzles are considered to the injector coking level for given fuel at the mean value of the air flow quantity reduction of 0.1mm needle lift.

Claims

1. a diesel fuel composition, it comprises Mannich reaction products between following as additive:

(a) aldehyde;

(b) amine; With

(c) substituted phenol;

Wherein said phenol is replaced by least one branched hydrocarbyl radical with 200-3000 molecular weight; And wherein, in being used to form the Mannich reaction of described additive, component (a) is 2.2-1.01:1 with the mol ratio of component (b); Component (a) is 1.99-1.01:1 with the mol ratio of component (c); And component (b) is 1:1.01-1.99 with the mol ratio of component (c).

2. the diesel fuel composition of claim 1, wherein the component (c) for the preparation of described Mannich additive comprises poly-(iso-butylene) derivative substituting group.

3. claim 1 or 2 diesel fuel composition, wherein in the reaction for the preparation of described Mannich additive, component (a) is 2-1.4:1 with the mol ratio of component (b), component (a) is 1.7-1.1:1 with the mol ratio of component (c), and component (b) is 1:1.1-1.7 with the mol ratio of component (c).

4. claim 1 or 2 diesel fuel composition, wherein in the reaction for the preparation of described Mannich additive, component (a) is 2-1.6:1 with the mol ratio of component (b), component (a) is 1.6-1.2:1 with the mol ratio of component (c), and component (b) is 1:1.1-1.5 with the mol ratio of component (c).

5. claim 1 or 2 diesel fuel composition, wherein in the reaction for the preparation of described Mannich additive, component (a) is 1.95-1.6:1 with the mol ratio of component (b), component (a) is 1.6-1.2:1 with the mol ratio of component (c), and component (b) is 1:1.15-1.5 with the mol ratio of component (c).

6. the diesel fuel composition of any one in aforementioned claim, wherein, in the reaction for the preparation of described Mannich additive, component (a) is 1.9-1.7:1 with the mol ratio of component (b).

7. the diesel fuel composition of any one in aforementioned claim, wherein, in the reaction for the preparation of described Mannich additive, component (a) is 1.5-1.3:1 with the mol ratio of component (c).

8. the diesel fuel composition of any one in aforementioned claim, wherein, in the reaction for the preparation of described Mannich additive, component (b) is 1:1.2-1.4 with the mol ratio of component (c).

9. the diesel fuel composition of any one in aforementioned claim; it further comprises quaternary ammonium salt additive, and described quaternary ammonium salt additive reacts by quaternizing agent and the acylating agent being replaced by alkyl and formula (B1) or amine (B2) the compound reaction forming and forms:

10. the diesel fuel composition of claim 6, wherein said quaternizing agent is selected from: the phosphoric acid salt that the carbonate that ester, dialkyl sulfate, benzyl halide, alkyl replace, the alkyl substituted epoxide with sour combination, alkylogen, alkylsulfonate, sultone, alkyl replace is, borate, alkyl nitride, alkyl nitrate, N-oxide compound or their mixture that alkyl replaces.

The diesel fuel composition of any one in 11. aforementioned claims, it also comprises fuel addition type catalyzer, and it comprises and is selected from following metal: iron, cerium, I Zu He II family metal, platinum, manganese and their mixture.

12. 1 kinds of additive-package, it provides the composition of any one in aforementioned claim after adding diesel-fuel to.

The method of 13. 1 kinds of operating diesel machines, described method is included in the composition of any one in the claim 1-8 that burns in described engine.

Mannich reaction products additive in 14. aforementioned claims in the diesel fuel composition of any one in order to improve the purposes of the motor performance of diesel engine when using described diesel fuel composition.

The purposes of 15. claims 12, in order to provide performance and/or " cleaning " performance of " keeping clean ".

The purposes of 16. claims 12 or claim 13, in order to improve the performance of the modern diesel engine with high-pressure fuel system and/or in order to improve the performance of conventional diesel engine.